U.S. patent number 5,079,093 [Application Number 07/465,237] was granted by the patent office on 1992-01-07 for easily-slippery medical materials and a method for preparation thereof.
This patent grant is currently assigned to Toray Industries, Inc.. Invention is credited to Ryojiro Akashi, Shoji Nagaoka.
United States Patent |
5,079,093 |
Akashi , et al. |
January 7, 1992 |
Easily-slippery medical materials and a method for preparation
thereof
Abstract
The present invention provides a medical material having an
easily-slippery property and durability which the conventional
technologies have never provided by fixing a hydrophilic polymer on
the surface of a base material through strong covalent bondings and
a method for preparation thereof.
Inventors: |
Akashi; Ryojiro (Kanagawa,
JP), Nagaoka; Shoji (Kanagawa, JP) |
Assignee: |
Toray Industries, Inc. (Tokyo,
JP)
|
Family
ID: |
26438092 |
Appl.
No.: |
07/465,237 |
Filed: |
June 4, 1990 |
PCT
Filed: |
August 09, 1989 |
PCT No.: |
PCT/JP89/00812 |
371
Date: |
June 04, 1990 |
102(e)
Date: |
June 04, 1990 |
PCT
Pub. No.: |
WO90/01344 |
PCT
Pub. Date: |
February 22, 1990 |
Foreign Application Priority Data
|
|
|
|
|
Aug 9, 1988 [JP] |
|
|
63-199294 |
Apr 17, 1989 [JP] |
|
|
1-96952 |
|
Current U.S.
Class: |
428/411.1;
427/407.1; 428/463; 428/520; 427/402; 428/424.4; 428/483 |
Current CPC
Class: |
A61L
29/085 (20130101); A61L 31/10 (20130101); A61L
27/34 (20130101); Y10T 428/31504 (20150401); Y10T
428/31797 (20150401); Y10T 428/31576 (20150401); Y10T
428/31928 (20150401); Y10T 428/31699 (20150401) |
Current International
Class: |
A61L
27/34 (20060101); A61L 29/08 (20060101); A61L
29/00 (20060101); A61L 27/00 (20060101); A61L
31/08 (20060101); A61L 31/10 (20060101); B32B
009/04 () |
Field of
Search: |
;604/265
;428/411.1,424.4,463,476.3,483,520 ;427/299,402,407.1 |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
|
|
|
|
|
|
|
A-0093093 |
|
Nov 1983 |
|
EP |
|
A-0106004 |
|
Apr 1984 |
|
EP |
|
0217771 |
|
Apr 1987 |
|
EP |
|
Primary Examiner: Cashion, Jr.; Merrell C.
Assistant Examiner: Nakarani; D. S.
Attorney, Agent or Firm: Nixon & Vanderhye
Claims
We claim:
1. A slippery medical material wherein the surface of a base
material coated with a component A is followed by a coating with a
component B, wherein said component A comprises a polymer having at
least one reactive functional group selected from the group
consisting of an alkali metal alcoholate group, amino group, an
alkali metal amide group, a carboxylic acid group, a sulfonic acid
group, a magnesium halide group and a fluorinated boron complex
group; and said component B comprises a hydrophilic polymer having
a reactive heterocyclic group being reactive with the reactive
functional group in the component A.
2. An easily-slippery medical material as described in claim 1
wherein the component A is a polymer having amino groups.
3. An easily-slippery medical material as described in claim 1
wherein the content of said reactive functional groups in the
component A is 0.1-50 wt.%.
4. An easily-slippery medical material as described in claim 1
wherein the reactive heterocyclic group in the component B is at
least one selected from the groups consisting of ethylene oxide
group, propylene oxide group, ethylene sulfide group, propylene
sulfide group, cyclooxabutane group, lactam and lactone groups of a
3 or 4 membered ring, amino acid-N-carboxylic acid anhydride group,
oxazolidine group, ethylene-imine group, propylene-imine group,
cyclic ether groups, cyclic azaether groups and cyclic thioether
groups.
5. An easily-slippery medical material as described in claim 1
wherein the reactive heterocyclic group in the component B is
ethylene oxide group.
6. An easily-slippery medical material as described in claim 1
wherein the content of the reactive heterocyclic group in the
component B is 0.01-50 wt.%.
7. An easily-slippery medical material as described in claim 1
wherein the component B is a copolymer consisting of a monomer
having a reactive heterocyclic group and a hydrophilic monomer.
8. An easily-slippery medical material as described in claim 7
wherein the hydrophilic monomer is at least one selected from the
group consisting of (meth)acrylamide, N-vinylpyrrolidone and
monomethoxytriethylene glycol mono(meth)acrylate.
9. A method of preparing a slippery medical material comprising the
steps of (1) applying to the surface of a base material a coating
of component A, and thereafter (2) applying thereover a coating of
component B, wherein said component A comprises a polymer having at
least one reactive functional group selected from the group
consisting of an alkali metal alcoholate group, an amino group, an
alkali metal amide group, a carboxylic acid group, a sulfonic acid
group, a magnesium halide group and a fluorinated boron complex
group; and said component B comprises a hydrophilic polymer having
a reactive heterocyclic group being reactive with the reactive
functional group in the component A.
10. A method for preparation of an easily-slippery medical material
as described in claim 9 wherein the component A is a polymer having
at least one reactive functional group selected among alkali metal
alcoholate groups, amino groups, alkali metal amide groups,
carboxylic acid group, sulfonic acid group, magnesium halide groups
and fluorinated boron complex groups.
11. A method for preparation of an easily-slippery medical material
as described in claim 9 wherein the component A is a polymer having
amino groups.
12. A method for preparation of an easily slippery medical material
as described in claim 9 wherein the content of said reactive
functional groups in the component A is 0.1-50 wt.%.
13. A method for preparation of an easily-slippery medical material
as described in claim 9 wherein the reactive heterocyclic group in
the component B is at least one selected from the groups consisting
of ethylene oxide group, propylene oxide group, ethylene sulfide
group, propylene sulfide group, cyclooxabutane group, lactam and
lactone groups of 3 or 4 membered ring, amino acid-N-carboxylic
acid anhydride group, oxazolidine group, ethylene-imine group,
propylene-imine group, cyclic ether groups, cyclic azaether groups
and cyclic thioether groups.
14. A method for preparation of an easily-slippery medical material
as described in claim 9 wherein the reactive heterocyclic group in
the component B is ethylene oxide group.
15. A method for preparation of an easily-slippery medical material
s described in claim 9 wherein the component B is a copolymer
consisting of a monomer having a reactive heterocyclic group and a
hydrophilic monomer.
16. A method for preparation of an easily-slippery medical material
as described in claim 15 wherein the hydrophilic monomer is at
least one selected from the group consisting of (meth)acrylamide,
N-vinyl-pyrrolidone and monomethoxy-triethylene glycol
mono(meth)acrylate.
17. A method for preparation of an easily-slippery medical material
as described in claim 9 characterized by using a peroxide, an azo
compound or a polymerizable polyfunctional monomer as a
crosslinking agent.
18. A method for preparation of an easily-slippery medical material
as described in claim 9 characterized by carrying out a
heat-treatment after coating with the component A and the Component
B.
19. A method for preparation of an easily-slippery medical material
as described in claim 18 characterized by carrying out a
heat-treatment at 30.degree.-200.degree. C. for 1 min-24 hr.
20. A method for preparation of an easily-slippery medical material
as described in claim 18 characterized by carrying out a
heat-treatment in an inert gas.
Description
TECHNOLOGICAL FIELD
The present invention relates to a medical material wherein a
hydrophilic coating exhibiting excellent low frictional property,
namely, easily-slippery property on wetting is formed on the
surface of a base material and a method for preparation
thereof.
BACKGROUND TECHNOLOGY
For medical materials including physiological and hygienic material
etc., especially for catheters and guide wires, low frictional
property (easily-slippery property) of the surface is one of the
essential requirements. For example, if these materials have no
easily-slippery property, when a catheter is inserted in a human
body, there is the possibility that a pain could be accompanied
with it or a damage or an inflammation of tissue mucosa could
occur.
As conventional technologies providing the easily-slippery
property, a method wherein the surface of a base material is coated
with a variety of oils, a method wherein the surface of the base
material is coated with a polymer having a low friction coefficient
such as Teflon and a method wherein it is coated with a hydrophilic
polymer are in public use. It is understood that especially,
coating with a hydrophilic polymer is superior one from the
viewpoints of practical use and safety.
As the practical methods for coating with a hydrophilic polymer,
fixation of polyvinyl pyrrolidone with an isocyanate (Japanese
Patent Laid-Open No.19,582/ 1984, U.S. Pat. No.4,100,309), a method
using a hydrophilic polymer copolymerized with a reactive
functional group and an isocyanate (Japanese Patent Laid-Open
No.81,341/1984), fixation of polyethylene oxide with an isocyanate
(Japanese Patent Laid-Open No.193,766/1983) are disclosed.
However, the method wherein the surface of a base material is
coated with a variety of oils exhibits low durability and has a
problem of safety due to eluates. The method wherein it is coated
with a polymer having a low friction coefficient such as Teflon
hardly exhibits sufficiently an easily-slippery property. The
method of coating with a hydrophilic polymer exhibits an
easily-slippery property being superior to these methods but there
is a problem on its durability. For example, in fixation of
polyvinylpyrrolidone with an isocyanate (Japanese Patent Laid-Open
No.19,582/1984, U.S. Pat. No.4,100,309), the bonding between
polyvinylpyrrolidone and the base material is not sufficient and an
eluation occurs. Furthermore, in an improved method thereof wherein
a hydrophilic polymer copolymerized with a reactive functional
group and an isocyanate are used (Japanese Patent Laid-Open
No.81,341/1984), these are not sufficiently solved. It is estimated
that this is caused by a relatively easy hydrolysis of the bonding
(amide bondings etc.). Moreover, in the fixation of polyethylene
oxide with an isocyanate (Japanese Patent Laid-Open No.193,766/
1983), there is similarly a problem on its durability.
As described above, there exists no method for providing an
easily-slippery property exhibiting both characteristics,
durability and safety. Namely, the purpose of the present invention
is to offer a technology providing an excellent easily-slippery
property which solves the problems of these conventional
technologies.
DISCLOSURE OF THE INVENTION
The present invention is an easily-slippery medical material
wherein the surface of a base material coated with the following
component A is coated with the following component B
Component A: A polymer having at least one reactive functional
group selected from alkali metal alcoholate groups, amino group,
alkali metal amide groups, carboxylic acid group, sulfonic acid
group, magnesium halide groups and fluorinated boron complex
groups.
Component B: A hydrophilic polymer having a reactive heterocyclic
group being reactive with reactive functional groups in the
component A. and the method of preparation thereof.
The best embodiment for Practicing the Invention
The present invention provides a medical material having excellent
easily-slippery property and durability which conventional
technologies have never been able to provide obtained by fixing a
hydrophilic polymer on the surface of a base material through a
covalent bonding and a method for preparation thereof.
The reactive functional group of the component A in the present
invention is such a group that can react with the reactive
heterocyclic group of the component B and those which are rich in
anionic or cationic characteristics so as to open the heterocyclic
ring are cited. As the practical example, alkali metal such as
lithium, sodium and potassium alcoholate groups, primary and
secondary amino groups, alkali metal amide groups, carboxylic acid
group, sulfonic acid group, Grignard reagents such as magnesium
halide group, fluorinated boron complex groups etc. can be cited.
Among them, amino groups are preferably used as they are highly
reactive.
As the polymer having such a reactive functional group, which is
the component A, partially hydrolyzed products with alkali of
polyvinyl acetate, hydrolyzed products with alkali of polymers
having vinyl acetate as a copolymerizable component, alkali-treated
products (alcoholates) of polymers having 2-hydroxyethyl
(meth)acrylate as a copolymerizable component, hydrolyzed products
(aminated products) of polyisocyanates, polymers having
aminomethylstyrene as a copolymerizable component and amidated
products thereof with alkali metals, polymers having styrene
derivatives containing various amino groups such as
2-aminoethyl-4-vinyl-phynetylamine as a copolymerizable component
and amidated products thereof with alkali metals, polymers having
(meth)acrylic acid as a copolymerizable component, polymers having
sulfonated styrene as a copolymerizable component, polymers having
chloromethyl styrene as a copolymerizable component Grignardized
with an active magnesium etc. are cited. As the practical examples,
alkali-hydrolyzates of ethylene-vinyl acetate copolymers, vinyl
chloride-vinyl acetate copolymers and methyl (meth)acrylate-vinyl
acetate copolymers and acrylonitrile-vinyl acetate copolymers,
alkali-treated products of methyl (meth)acrylate-2-hydroxyethyl
(meth)acrylate copolymers, styrene-2-hydroxyethyl (meth)acrylate
copolymers, acrylonitrile-2-hydroxyethyl (meth)acrylate copolymers,
styrenehydroxystyrene copolymers and methyl
(meth)acrylatehydroxystyrene copolymers, hydrolyzates (aminated
products) of adducts of diphenylmethane-4,4'-diisocyanate or
hexamethylenediisocyanate with trimethylolpropane and adducts of
tolylene diisocyanate with trimethylolpropane,
styrene-aminomethyl-styrene copolymers, methy
(meth)acrylate-aminomethylstryene copolymers,
styrene-2-aminoethyl-4-vinylphenetylamine copolymers, methyl
(meth)-acrylate-2-aminoethyl-4-vinylphenylamine copolymers,
vinylidene chloride-2-aminoethyl-4-vinylphenetylamine copolymers
and acrylonitrile-2-aminoethyl-4-vinylphenetylamine copolymers and
their amidated products with alkali metals (for example, lithium,
sodium and potassium), acrylonitirle-(meth)acrylic acid copolymers,
vinyl chloride-(meth)acrylic acid copolymers, vinylidene
chloride-(meth)acrylic acid copolymers, methyl
(meth)acrylate-(meth)acrylic acid copolymers,
ethylene-(meth)acrylic acid copolymers, styrene-(meth)acrylic acid
copolymers, and furthermore, Grignardized products of
styrene-chloromethylstyrene copolymers, methyl
(meth)acrylate-chloromethylstyrene copolymers, vinylidene
chloride-chloromethylstyrene copolymers and
acrylonitrilechloromethylstyrene copolymers are cited.
The content of said reactive functional groups in said component A
is variably selected in accordance with the bonding force with the
component B and the adhesive force and preferably selected in the
range of 0.1-50 wt.%. The range of 1 - 30% is especially
preferable. As the reactive heterocyclic group in the component B
in the present invention, any heterocyclic group which can react
with the reactive functional group of the coponent A can be used,
but those ring structures which have high strain are preferable
from the viewpoint of high reactivity. As the practical examples,
ethylene oxide group, propylene oxide group, ethylene sulfide
group, propylene sulfide group, cyclooxabutane group, Lactam and
Lactone groups of a 3 or 4 membered ring, amino acid-N-carboxylic
acid anhydride group (NCA), oxazolidine group, ethylene-imine
group, propylene-imine group, cyclic ether groups such as dioxane,
trioxane and tetraoxane cyclic azaether groups and thioether groups
are cited. Ethylene oxide group is especially preferably selected
as it is easily used.
The content of said reactive heterocyclic group in said component B
is variably selected in accordance with the aimed characteristics,
0.01-50 wt.%, especially 0.1-30 wt.% is preferable in terms of the
amount of the side chains containing the reactive heterocyclic
group.
The hydrophilic polymers having said reactive heterocyclic groups,
which are the component B, can be prepared by either of the
following methods, namely, a method (1) wherein a monomer having a
reactive heterocyclic group is copolymerized with a hydrophilic
monomer and a method (2) wherein a compound having a reactive
heterocyclic group is reacted with and thereby introduced in a
hydrophilic polymer.
As the practical examples of the method (1),
(meth)acrylamide-glycidyl (meth)acrylate copolymers,
N-vinyl-2-pyrrolidone-glycidyl (meth)acrylate copolymers,
monomethoxytriethylene glycol mono(meth)acrylate-glycidyl
(meth)acrylate copolymers, monomethoxytetraethylene glycol
mono(meth)acrylate-glycidyl (meth)acrylate copolymers, polyethylene
glycol mono(meth)acrylate-glycidyl (meth)acrylate copolymers,
2-hydroxyethyl (meth)acrylateglycidyl (meth)acrylate copolymers,
(meth)acrylamideglycidyl vinyl benzoate copolymers,
N-vinylpyrrolidoneglycidyl vinyl benzoate copolymers, polyethylene
glycol mono(meth)acrylate-glycidyl vinyl benzoate copolymers and
2-hydroxyethyl (meth)acrylate-glycidyl vinyl benzoate copolymers
are representative ones, and any hydrophilic polymer obtained by
copolymerizing a monomer providing hydrophilic nature such as
(meth)acrylamide, N-vinylpyrrolidone, monomethoxytriethylene glycol
mono(meth)acrylate, monomethyorytetraethylene glycol
mono(meth)acrylate, polyethylene glycol mono(meth)acrylate having a
molecular weight of 500-10,000, 2-hydroxyethyl (meth)acrylate,
glyceryl (meth)acrylate, (meth)acrylic acid or its salts,
2-vinylpyridine and N-1,2,4-triazolyethylene with a reactive
heterocyclic vinyl monomer of the following general formulas
(I)-(V) can be used. The content of the reactive heterocyclic vinyl
monomer is properly selected in accordance with the aimed
characteristics and it is preferably in the range of 0.01-50 wt.%
not to spoil the hydrophilic nature. Moreover, to impart physical
strength to the hydrophilic polymer, it is preferably to
copolymerize a hydrophobic monomer as the third component. In this
case, the content of the third component is not specifically
restricted as far as the hydrophilic nature is not spoiled, but the
range of 0.01-50 wt.% is preferable. As the practical examples of
the hydrophobic monomers which can be used, alkyl (meth)acrylates,
vinyl chloride, vinylidene chloride, ethylene, (meth)acrylonitrile,
propylene, vinyl acetate, styrene and styrene derivatives are
cited. Moreover, as the molecular weight of these polymers,
polymers having a molecular weight of 1,000-5,000,000 can be used
and 100,000-2,000,000 is preferable.
As the practical examples of the method (2), compounds wherein a
part of hydroxyl groups or amino groups contained in hydrophilic
polymer such as cellulose, cellulose derivatives (methyl cellulose,
ethyl cellulose, ##STR1## carboxymethylcellulose,
cyanoethylcellulose, cellulose acetate,sodium salt of cellulose
nitrate), amylose, amylopectin, alginic acid, heparin, pectin and
water-soluble nylon are reacted with a compound of the following
formula (VI) and a reactive heterocyclic ring is thereby
introduced, are cited. In this case, the content of introduction of
the reactive heterocyclic ring is not especially restricted as far
as the aimed hydrophilic nature is not spoiled, but the range of
0.01-50 wt.% is preferable. ##STR2##
The hydrophilic coatings of the present invention have good
easily-slippery property and durability caused by said
constitution, but it is a desirable method to cure the component B
after coating for improving the durability furthermore. Namely, it
is possible to improve the physical strength without lowering the
easily-slippery property by providing a three dimensional network
structure. As the method for curing (crosslinking) like this, it is
possible to apply generally various physicochemical means. For
example, a method wherein said polymer is cured (crosslinked) by
generating active radicals by using light, heat or radiation and
moreover, a polymerizable polyfunctional monomer is therein
additionally added. As a method for generating efficiently active
radicals, it is preferable to use peroxides and azo compounds. It
is especially preferable to use peroxides having a strong
capability of drawing hydrogen. As the practical examples, acetyl
peroxide, cumyl peroxide, propionyl peroxide, benzoyl peroxide,
tert-butyl performate, potassium persulfate etc. are cited. The
loading of these compounds to the component B is properly selected
in accordance with the aimed characteristics, but the range of
0.001-20 wt.% is preferable. Moreover, as the practical examples of
polymerizable polyfunctional monomer which can be incorporated to
cure (crosslink) furthermore efficiently, divinylbenzene, ethylene
glycol di(meth)acrylate, trimethylolpropane or pentaerythritol di-,
tri- or tetra- (meth)acrylate, diethylene glycol or polyethylene
glycol di(meth)acrylate can be cited. The loading of these
compounds to the component B is properly selected in accordance
with the aimed characteristics, but the range of 0.1-30 wt.% is
preferably selected.
Next, the method for forming the medical materials having
easily-slippery property of the present invention will be explained
in more detail.
The base material is variably selected in accordance with the
purpose of use and various plastics, inorganic materials and
metallic materials are suitably used. As the practical examples,
polyvinyl chloride, polyethylene, polypropylene, polystyrene,
polyurethane, polyurea, polymethyl methacrylate, nylon, polyester,
polyacrylonitrile, metallic wires coated therewith, stainless
steel, elastic metals, ceramics and wood are cited.
As the methods for coating the surfaces of these base materials
with the component A, it is preferable that dipping or spin coating
is carried out by using a solution wherein a specified amount of
the component A is dissolved in a proper good solvent and then
drying is done. As the solvents to be used, alcohols, aromatic
hydrocarbons, linear or cyclic hydrocarbons, halogenated
hydrocarbons, ketones and amides are preferable. The concentration
of the component A in the solution can be properly selected in
accordance with the aimed thickness of coating, but the range of
0.01-50 wt.% is preferably used. The range of 1-10 wt.% is
especially preferable.
Then, the surface of a base material coated with the component A is
coated with the component B. The method of coating is the same as
the method of coating for the component A, namely, dipping or spin
coating is carried out by using a solution wherein a specified
amount of the component B is dissolved in a proper good solvent and
then drying is done. As the solvents, besides said solvent, water
can be also used. The concentration of the component B in the
solution can be properly selected in accordance with the aimed
thickness of coating, but the range of 0.01-50 wt.% is preferably
used. The range of 1-10 wt.% is especially preferable. When a
curing (crosslinking) agent such as peroxides, azo compounds and
polymerizable polyfunctional monomers is used, it is preferable
that the specified amount thereof is added in this solution.
After coatings with the component A and the component B, a reaction
of the component A with the component B is carried out by carrying
out successively by a heat treatment. The heating condition, the
time and the temperature are properly selected in accordance with
the nature of the reaction and existence of a curing (crosslinking)
reaction and one of the preferable range is 30.degree.-200.degree.
C. and 1 min-24 hr. It is also a preferable method to carry out the
reaction in various inert gases for suppressing side reactions.
"Examples"
The present invention will be explained in more detail heretobelow
by examples, but is not restricted thereby.
EXAMPLE 1
As a component B, acrylamide-glycidyl methacrylate copolymer having
a molecular weight of about 200,000 was obtained by polymerizing
9.0 g of acrylamide and 1.0 g of glycidyl methacrylate in dimethyl
sulfoxide (DMSO) by using AIBN (azobisisobutyronitrile) as an
initiator.
A wire having a diameter of 2 mm prepared by coating a stainless
wire with a polyurethane was immersed in a 2% polyisocyanate
(manufactured by Nippon Polyurethane Industries Co., Ltd., The name
of the product: C-L, TDI/TMP adduct) solution in methyl ethyl
ketone (MEK) for 1 min and the coated wire was dried at 50.degree.
C. for 1 hr. Then, this was immersed in 0.1 N sodium hydroxide ag.
solution at 40.degree. C. for 1 hr to hydrolyze it and to form
amino groups.
Then, this wire was immersed in a 5% acrylamideglycidyl
methacrylate copolymer aq. solution for 5 sec and pulled up and the
reaction was carried out at 100.degree. C. for 5 hr.
The obtained wire coated with the hydrophilic coating exhibited
excellent easily-slippery property when it was wetted with a
physiological saline or water and also exhibited excellent
easily-slippery property after 1 hr boiling, which meant excellent
durability.
EXAMPLE 2
As a component A, methyl methacrylate-2-hydroxyethyl methacrylate
copolymer having a molecular weight of about 100,000 was obtained
by polymerizing 8.0 g of methyl methacrylate and 2.0 g of
2-hydroxyethyl methacrylate in isopropyl alcohol by using AIBN
(azobisisobutyronitrile) as an initiator.
Then, the same wire as that of Example 1 was immersed in a 3%
solution of this polymer in dioxane for 1 min and dried at
50.degree. C. for 1 hr. Furthermore, this was immersed in 1 N
sodium hydroxide aqueous solution to form sodium alcoholate.
Then, as a component B, the same compound as that of Example 1 was
used and was reacted by means of the same method.
The obtained wire coated with the hydrophilic coating exhibited
excellent easily-slippery property when it was wetted with a
physiological saline or water and also exhibited excellent
easily-slippery property after 1 hr boiling, which meant excellent
durability.
EXAMPLE 3
As a component B, N-vinylpyrrolidone-glycidyl acrylate copolymer
having a molecular weight of about 300,000 was obtained by
polymerizing 9.0 g of N-vinylpyrrolidone and 1.0 g of glycidyl
acrylate by using V-65 (azobisvaleronitrile) as an initiator.
The same treatment as that of Example 1 was performed by using the
same materials as those of Example 1 as both a component A and a
base material (wire).
Then, this wire was immersed in 3% solution of the previously
synthesized N-vinylpyrrolidone-glycidyl acrylate copolymer in
chloroform for 5 sec, pulled out therefrom, dried and reacted at
100.degree. C. for 5 hr.
The obtained wire coated with the hydrophilic coating exhibited
excellent easily-slippery property when it was wetted with a
physiological saline or water and also exhibited excellent
easily-slippery property after 1 hr boiling, which meant excellent
durability.
EXAMPLE 4
A hydrophilic coating was formed by the same method as that of
Example 3 except using N-vinylpyrrolidone-vinyl acetate-glycidyl
acrylate copolymer having a molecular weight of about 500,000
obtained by polymerizing 7.0 g of N-vinylpyrrolidone, 2.0 g vinyl
acetate and 1.0 g of glycidyl acrylate in ethyl alcohol by using
V-65 (azobisvaleronitrile) as an initiator as a component B.
The obtained wire exhibited excellent easily-slippery property when
it was wetted with a physiological saline or water and it was found
that it exhibited excellent easily-slippery property after 1 hr
boiling and had excellent durability.
EXAMPLE 5
A hydrophilic coating was formed by the same method as that of
Example 3 except using N-vinylpyrrolidone-ethyl acrylate-lycidyl
acrylate copolymer having a molecular weight of about 600,000
obtained by polymerizing 8.0 g of N-vinylpyrrolidone, 1.5 g of
ethyl acrylate and 0.5 g of glycidyl acrylate in isopropyl alcohol
by using V-65 as an initiator as a component B. In this Example, a
procedure wherein after heat-reaction for 1 hr, it was immersed in
water for 1 min and then heat-reaction was performed again, was
furthermore added.
The obtained wire exhibited excellent easily-slippery property when
it was wetted with a physiological saline or water and it was found
that it exhibited excellent easily-slippery property after 1 hr
boiling and had excellent durability.
EXAMPLE 6
As a component B, monomethoxytetraethylene glycol
monomethacrylate-glycidyl vinyl benzoate copolymer having a
molecular weight of about 1000,000 was obtained by polymerizing 9.5
g of monomethoxytetraethylene glycol monomethacrylate and 0.5 g of
glycidyl vinyl benzoate in tetrahydrofuran by using AIBN
(azobisisobutyronitrile) as an initiator.
The same component A and base material (wire) as those of Example 2
were used and treated with the same method as that of Example 2.
Then, this wire was immersed in 5% previously synthesized
monomethoxytetraethylene glycol monomethacrylate-glycidyl vinyl
benzoate copolymer solution in dimethylacetamide for 5 sec, pulled
up, dried and reacted at 100.degree. C. for 5 hr.
The obtained wire exhibited excellent easily-slippery property when
it was wetted with a physiological saline or water and it was found
that it exhibited especially excellent easily-slippery property
after 1 hr boiling and had excellent durability.
EXAMPLE 7
A hydrophilic coating was formed by the same method as that of
Example 3 except adding 1% of benzoyl peroxide (based on the
polymer) to N-vinylpyrrolidone-glycidyl acrylate copolymer and
carrying out the reaction under reaction conditions which were at
120.degree. C., for 5 hr under nitrogen atmosphere.
The obtained wire exhibited excellent easily-slippery property when
it was wetted with a physiological saline or water and it was found
that it exhibited especially excellent easily-slippery property
after 1 hr boiling and had excellent durability.
EXAMPLE 8
A hydrophilic coating was formed by the same method as that of
Example 4 except adding 1% of benzoyl peroxide (based on the
polymer) and 5% of tetraethylene glycol dimethacrylate (based on
the polymer) to N-vinylpyrrolidone-vinyl acetate-glycidyl acrylate
copolymer used in Example 4 and carrying out the reaction under
reaction conditions which were at 120.degree. C. for 5 hr under
nitrogen atmosphere.
The obtained wire exhibited excellent easily-slippery property when
it was wetted with a physiological saline or water and it was found
that it exhibited especially excellent easily-slippery property
after 1 hr boiling and had excellent durability.
COMPARATIVE EXAMPLE 1
The same polyurethane-coated wire as that of Example was immersed
in 2% polyisocyanate (manufactured by Nippon Polyurethane
Industries Co., Ltd., The name of the product: C-L, TDI/TMP adduct)
solution in methyl ethyl ketone (MEK) for 1 min and dried at
50.degree. C. for 1 hr. Then, this was immersed in 4%
polyvinylpyrrolidone (manufactured by Polysciences, Inc., the
molecular weight was 360,000) solution in chloroform for 5 sec,
pulled up, dried and then reached at 80.degree. C. for 5 hr. When
the obtained wire was wetted with a physiological saline or water,
it exhibited excellent easily-slippery property at the beginning,
but after a repeated test of several times or boiling for several
min, it exhibited no easily-slippery property at all and as the
result, it was found that the durability was poor.
Comparative Example 2
A sample was prepared by the same method as that of Comparative
Example 1 except using polyethylene glycol (the molecular weight
was 6,000) as a hydrophilic polymer. The obtained wire did not
exhibit good easily-slippery property when it was wetted with a
physiological saline or water and it became not to exhibit
easily-slippery property at all after a repeated test of several
times or boiling for several min and as the result, it was found
the durability was poor.
The results of evaluation in Examples 1-8 and Comparative Example 1
and 2 are shown in Table 1.
TABLE 1 ______________________________________ Evaluation
Easily-slippery property No. Initial After boiling for 1 hr
______________________________________ Example 1 .smallcircle.
.smallcircle. 2 .smallcircle. .smallcircle. 3 .circleincircle.
.smallcircle. 4 .circleincircle. .circleincircle. 5
.circleincircle. .circleincircle. 6 .circleincircle. .smallcircle.
7 .circleincircle. .circleincircle. 8 .circleincircle.
.circleincircle. Comparative example 1 .circleincircle. x 2 .DELTA.
x ______________________________________ .circleincircle.:
Especially good, .smallcircle.: Good, .DELTA.: Average, x: poor
Possibility of Industrial Application
The easily-slippery material of the present invention can be widely
applicable in a variety of fields. Above all, as this material has
both excellent easily-slippery property and durability (safety), it
is applicable for medical materials such as catheters, guide wires,
endoscopes, contact lenses and condom. Moreover, it has excellent
biocompatibility as it has a hydrophilic nature and when it is
applied for medical materials, it is expected that besides said
characteristics, such excellent characteristics as high
anti-thrombus characteristics can be obtained.
* * * * *